A Fundamental Role of the Molecular Length in Forming Metal-Organic Hybrids of Phenol Derivatives on Silver Surfaces.

In on-surface chemistry, the efficient preparation of metal-organic hybrids is regarded as a primary path to mediate controlled synthesis of well-ordered low-dimensional organic nanostructures. The fundamental mechanisms in forming these hybrid structures, however, are so far insufficiently explored. Here, with scanning tunneling microscopy, we studied the bonding behavior of the adsorbed phenol derivatives with different molecular lengths. We reveal that shorter molecules favor bonding with extracted metal adatoms and result in metal-organic hybrids, whereas longer molecules prefer to bond with lattice metal atoms. The conclusions are further confirmed by density functional theory calculations.